Anode active material for secondary battery

ABSTRACT

Disclosed is an anode active material including: a crystalline phase comprising Si and a Si-metal alloy; and an amorphous phase comprising Si and a Si-metal alloy, wherein the metal of the Si-metal alloy of the crystalline phase is the same as or different from the metal of the Si-metal alloy of the amorphous phase.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a national phase entry under 35 U.S.C. §371of International Application No. PCT/KR2009/007985, filed Dec. 30, 2009,published in Korean, which claims priority from Korean PatentApplication No. 10-2008-0136721, filed Dec. 30, 2008. The disclosures ofsaid applications are incorporated by reference herein.

TECHNICAL FIELD

The present disclosure relates to an anode active material for asecondary battery exhibiting superior cycle characteristics, less volumeexpansion and high capacity.

BACKGROUND

Recently, with the development of mobile applications, high-capacityenergy source is required. The lithium secondary battery is arepresentative example. In the currently used lithium secondary battery,carbonaceous materials are used as anode active material. Thetheoretical capacity of the carbonaceous material is 372 mAh/g. Sincethe capacity of the presently commercially available batteries is around360 mAh/g, it has almost reached the theoretical capacity limit.Accordingly, for preparation of high-capacity batteries, development ofa new material capable of replacing the carbonaceous anode activematerial is necessary.

Representative materials as the new high-capacity anode active materialinclude metallic materials such as silicon (Si), tin (Sn), etc. thatallow intercalation/deintercalation of lithium (Li) via alloyingreactions with lithium. However, when a metal such as silicon (Si), tin(Sn), etc. alone is used as the anode active material, volume changeduring charging-discharging is very large, as much as 300-400%,resulting in separation from the electrode and significant deteriorationof cycle characteristics. Therefore, it is hard to be actually appliedin batteries.

To overcome this problem, alloys of silicon (Si) or tin (Sn) with othermetals (i.e., Si-M alloys and Sn-M alloys, M is a metal element) havebeen studied by many researchers. These alloy-type materials are knownto form a single-element phase of silicon (Si), tin (Sn), etc. that canbind with lithium, a metal silicide (M_(x)Si_(y)) phase that does notbind with lithium, a metal-tin (Sn) alloy (M_(x)Sn_(y)) phase, or thelike. The single phase of silicon (Si), tin (Sn), etc. is capable ofbinding with and release from lithium during charging-discharging and,thus, provides battery capacity through electrochemical reactions. Themetal silicide (M_(x)Si_(y)) phase and the metal-tin (Sn) alloy(M_(x)Sn_(y)) phase do not bind with lithium but are known to suppressvolume expansion of the anode active material by suppressing the volumechange of the single phase of silicon (Si), tin (Sn), etc.

In this regard, in order to control electric capacity and cyclecharacteristics, the phases of the anode active material have beendivided into a phase mainly essentially of Si and a phase mainlyconsisting of Si-metal alloy, and the ratio of the phases (JapanesePatent Laid-Open No. 2006-164960), or the particle size of the phases(Japanese Patent No. 4344121, Korean Patent No. 911799) have beencontrolled.

However, in spite of these efforts, the electric capacity and cyclecharacteristics are not satisfactorily controlled. Accordingly, there isa need of an anode active material allowing a better control of theseproperties.

SUMMARY

Although there have been efforts to divide a Si phase and a Si-metalalloy and control their ratio, a material including both a crystallinephase and an amorphous phase of Si and Si-metal alloy has never beenreported.

The inventors of the present disclosure have found out that a Si-metalalloy used to suppress volume expansion of an anode active materialexists as a crystalline phase as well as an amorphous phase and that theSi single phase existing separately from the Si-metal alloy contributesto electric capacity even though it is an amorphous phase.

Conventionally, it was thought that the Si contributing to electriccapacity exists only as a crystalline phase and that an amorphous phaseis composed of Si-metal alloy and thus cannot contribute to electriccapacity. Accordingly, although there have been attempts to control theratio of the Si phase and the Si-metal alloy or particle size thereof toimprove electric capacity and cycle characteristics of a battery, noattempt has been made to control the ratio of the crystalline phase andthe amorphous phase. However, according to the researches performed bythe inventors of the present disclosure, the electric capacity and cyclecharacteristics cannot be improved sufficiently with the conventionalmethods, since the Si existing in the amorphous phase also contributesto the electric capacity.

In a general aspect, the present disclosure provides an anode activematerial including: a crystalline phase comprising Si and a Si-metalalloy; and an amorphous phase comprising Si and a Si-metal alloy,wherein the metal of the Si-metal alloy of the crystalline phase is thesame as or different from the metal of the Si-metal alloy of theamorphous phase.

In another general aspect, the present further provides an electrodeincluding the anode active material, and a lithium secondary batteryincluding the electrode. In another general aspect, the presentdisclosure further provides an electrode including the anode activematerial as well as a carbonaceous anode active material, and a lithiumsecondary battery including the electrode.

Other features and aspects will be apparent from the following detaileddescription, the drawings, and the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other objects, features and advantages of the presentdisclosure will become apparent from the following description ofcertain exemplary embodiments given in conjunction with the accompanyingdrawings, in which:

FIG. 1 shows an X-ray diffraction (XRD)-Rietveld refinement result of aSi—Ni—Ti alloy (Composition, weight ratio and preparation method aredescribed in Example 1);

FIG. 2 shows an XRD-Rietveld refinement result of the alloy of FIG. 1after adding 20% of MgO to mix the anode active material with MgO at aweight ratio of 8:2; and

FIG. 3 shows cycle characteristics of the anode active materials ofExamples 1-5 and Comparative Example 1.

DETAILED DESCRIPTION OF EMBODIMENTS

The advantages, features and aspects of the present disclosure willbecome apparent from the following description of the embodiments withreference to the accompanying drawings, which is set forth hereinafter.The present disclosure may, however, be embodied in different forms andshould not be construed as limited to the embodiments set forth herein.Rather, these embodiments are provided so that this disclosure will bethorough and complete, and will fully convey the scope of the presentdisclosure to those skilled in the art. The terminology used herein isfor the purpose of describing particular embodiments only and is notintended to be limiting of the example embodiments. As used herein, thesingular forms “a”, “an” and “the” are intended to include the pluralforms as well, unless the context clearly indicates otherwise. It willbe further understood that the terms “comprises” and/or “comprising”,when used in this specification, specify the presence of statedfeatures, integers, steps, operations, elements, and/or components, butdo not preclude the presence or addition of one or more other features,integers, steps, operations, elements, components, and/or groupsthereof.

Hereinafter, exemplary embodiments will be described in detail withreference to the accompanying drawings.

The present disclosure provides an anode active material including: acrystalline phase comprising Si and a Si-metal alloy; and an amorphousphase comprising Si and a Si-metal alloy.

In the anode active material, the metal of the Si-metal alloy of thecrystalline phase may be the same as or different from the metal of theSi-metal alloy of the amorphous phase.

In the Si-metal alloy of the crystalline phase and the Si-metal alloy ofthe amorphous phase, the metal may comprise one or more metal species.Preferably, it may comprise two or more metal species. That is to say,the alloy may be in the form of Si-A, Si-A-B, Si-A-B—C, and so forth(wherein A, B and C denote different metals).

The metal may be Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr,Nb, Ba, Lu, Hf, Ta or lanthanides. Preferably, Ca, Co, Ni, Mn, Ti, Zr,Co, Ni, Fe or rare earth elements (Sc, Y and lanthanides) may be usedamong them.

In case of a Si-A type alloy comprising one metal in addition to Si, themetal may be selected from Co, Ni, Mn and Ti.

In case of a Si-A-B type alloy comprising two metals in addition to Si,A may be a metal selected from Ti and Zr, and B may be a metal selectedfrom Co, Ni and Fe.

In addition, one or more metal selected from rare earth elements may bemixed with a metal selected from Co, Ni and Fe. In this case, the rareearth element may be a mixed rare earth element, preferably misch metal.

In the present disclosure, the anode active material comprises acombination of the crystalline phase and the amorphous phase. Both thecrystalline phase and the amorphous phase comprise a material allowingrepetitive intercalation and deintercalation of Li electrochemically anda material incapable of binding with Li electrochemically. Thecrystalline phase comprises Si and a Si-metal alloy. The crystallinephase may further comprise other metals. The amorphous phase alsocomprises Si and a Si-metal alloy. The amorphous may further compriseother metals.

In the present disclosure, Si and the Si-metal alloy are present both inthe crystalline phase and the amorphous phase, and the ratio of the twophases is controlled to minimize volume expansion and maximize cyclecharacteristics. The ratio of the crystalline phase and the amorphousphase may be controlled by varying the kind and amount of the metal, themethod of preparing the alloy, or the like. The amount of the amorphousphase may be controlled by ball milling, which is a mechanical alloyingmethod. For example, the amount of the amorphous phase may be increasedby selecting a composition allowing easy formation of the amorphousphase, increasing cooling speed during quenching, or increasing ballmilling time, ball-to-alloy ratio, linear speed of the milling machine,or the like.

In the anode active material of the present disclosure, the amount ofthe amorphous phase may be 30 wt % or more based on the crystallinephase and the amorphous phase combined. The higher the content of theamorphous phase, the better.

The source material for preparing the anode active material is notparticularly limited in form as long as the desired composition can beachieved. For example, the source material may be in the form ofelement, alloy, solid solution, intermetallic compound, or the like.

The method for preparing the anode active material according to thepresent disclosure is not particularly limited as long as a uniformmixture of the crystalline phase and the amorphous phase can beobtained. For example, melt spinning whereby a composition comprising Siis melted and then quenched, strip casting, atomization, or the like maybe employed. In addition, direct cast-rolling, spray foaming, gasspraying, wet spraying, or the like may also be employed. Thus preparedalloy is pulverized to prepare a metal powder comprising Si. Theresulting metal powder is mechanically ground to prepare the anodeactive material. Preferably, the particle size may be from 1 μm to 50μm.

The resultant alloy phase may be treated by mechanical alloying toobtain the anode active material with a desired ratio of the crystallinephase and the amorphous phase.

The present disclosure also provides an electrode comprising the anodeactive material, and a lithium secondary battery comprising theelectrode. The present disclosure further provides an electrodecomprising the anode active material as well as a carbonaceous anodeactive material, and a lithium secondary battery comprising theelectrode.

The anode active material may be used to prepare an electrode. Theelectrode may be prepared by mixing the metal powder with a conductingagent and a binder. The binder may be polyvinylidene fluoride (PVDF) orany other binder as long as the electrode can be formed. For example,polyethylene, polypropylene, polytetrafluoroethylene, styrene-butadienerubber, or the like may be used.

After the binder is dissolved in a solvent such as NMP, the metal powderand the conducting agent are added together to form a homogeneousslurry. The conducting agent may be acetylene black. However, otherconducting agents such as artificial graphite, carbon fiber, carbonnanotube (CNT), amorphous carbon, etc. may be used as long as theconductivity of the electrode can be ensured.

With the previously known Rietveld refinement by X-ray diffraction (XRD)patterns, it is difficult to accurately measure the amount of theamorphous phase in the anode active material of the present disclosure.It is because although the Rietveld refinement gives information aboutthe exact content of the crystalline phase it does not inform thecontent of the amorphous phase.

Thus, in the present disclosure, a method of mixing the active materialwith a predetermined amount of a known standard material, performingXRD-Rietveld refinement to calculate the volume ratio of respectivephases, and calculating the contents of the phases from that of thestandard material. This method is called spiking.

Details are as follows.

<XRD-Rietveld Refinement>

XRD-Rietveld refinement result of a Si—Ni—Ti alloy (Composition, weightratio and preparation method are described in Example 1) is shown inFIG. 1. Based on the result, the contents of respective phases arecalculated as follows.

TABLE 1 Phases wt % Si 36.5 Si₂Ti 57 Ti₄Ni₄Si₇ 3.23 Ni₃Si 0.67 a-Ti 2.58

From the content of Si in the alloy, 36.5 wt %, the electric capacity iscalculated as 1315 mAh/g. However, the experimentally measured electriccapacity of the alloy is 1100 mAh/g, much smaller than the theoreticalvalue. This shows that the amount of Si participating in the reactioncannot be exactly determined through simple XRD-Rietveld refinement.

<Spiking>

XRD-Rietveld refinement result of the alloy of FIG. 1 after adding 20%of MgO with excellent crystallinity and having XRD peaks not overlappingwith those of the observed peaks, to mix the anode active material withMgO at a weight ratio of 8:2 is shown in FIG. 2. Based on the result,the contents of respective phases are calculated as follows.

TABLE 2 Phases wt % (with MgO) wt % (without MgO) Si 16.3 20.4 Si₂Ti24.1 30.1 Ti₄Ni₄Si₇ 1.0 1.2 Ni₃Si 0.3 0.3 a-Ti 1.1 1.4 MgO 20.0 —Amorphous 37.3 46.6

When MgO is added, the amount of Si in the alloy is 16.3 wt % and thatof the amorphous phase is 37.3 wt %. After removal of the standardmaterial MgO, the amount of Si is calculated as 20.4 wt % and that ofthe amorphous phase is calculated as 46.6% wt %.

From the content of Si, 20.4 wt %, obtained by the spiking method, theelectric capacity is calculated as 735 mAh/g. This is smaller than theexperimentally measured value 1100 mAh/g by 365 mAh/g. It suggests thatthe Si included in the amorphous phase also contributes to the electriccapacity.

Accordingly, it can be seen that Si and the Si-metal alloy are includednot only in the crystalline phase but also in the amorphous phase.Further, it can be seen that when the crystalline phase and theamorphous phase exist together, both the crystalline phase and theamorphous phase include Si and the Si-metal alloy. Accordingly, it canbe seen that both the crystalline phase and the amorphous phasecontribute to electric capacity.

EXAMPLES

The examples and experiments will now be described. The followingexamples and experiments are for illustrative purposes only and notintended to limit the scope of this disclosure.

Example 1

1. Preparation of Anode Active Material

After mixing Si, Ni and Ti at a weight ratio of 60:5:35, a metal ribbonwas prepared by melt spinning. The melt spinning was performed using acarbon crucible under a non-oxidizing inert atmosphere by injectingargon gas. The prepared metal ribbon was crushed manually in a mortar toproduce a metal powder, which was sieved so that the particle size wasnot greater than 38 μm.

2. Phase Analysis by XRD and Spiking

The phases of the metal powder were analyzed by XRD. The Bruker AXS D4Endeavor XRD analyzer, wavelength of 1.94 Å (Fe K α), and the LynxEyeposition sensitive detector were used.

Spiking analysis was performed to accurately analyze the ratio of thecrystalline phase and the amorphous phase. The metal powder preparedabove was uniformly mixed with 20% of MgO in a mortar and XRDmeasurement was made in the same manner as described above. Then,Rietveld refinement was carried out to accurately determine the fractionof the crystalline phase and MgO in the material. From the result, thefraction of the amorphous phase was calculated.

3. Preparation of Electrode and Battery

An electrode was prepared using the anode active material preparedabove. The electrode was prepared by mixing the metal powder with aconducting agent and a binder. PVDF was used as the binder. Afterdissolving PVDF in NMP, the metal powder and the conducting agent wereadded together to prepare a homogeneous slurry. For the conductingagent, acetylene black was used. The weight ratio of the metal powder,the conducting agent and the binder in the electrode slurry was80:10:10. The prepared slurry was applied well on a copper foil and thendried at 130° C. under a vacuum atmosphere for 4 hours.

Then, a coin half cell was prepared using the electrode and metallic Li.For the preparation of the coin cell, an electrolyte comprising 1 MLiPF₆ dissolved in a mixture of ethylene carbonate and diethyl carbonate(3:7) was used. A separator was placed between the metallic Li and theelectrode.

4. Evaluation of Battery Performance (Electric Capacity, CycleCharacteristics and Volume Expansion)

Electric capacity and cycle characteristics of the anode active materialwere evaluated using the prepared coin cell.

After charging for 50 cycles, the coin cell was disassembled and thechange in thickness was measured.

Examples 2-5

The ratio of the crystalline phase and the amorphous phase of the metalpowder prepared in Example 1 was varied by ball milling (using SPEX MILL8000). The ball milling was performed for 30 hours (Example 2), 60 hours(Example 3), 90 hours (Example 4) or 120 hours (Example 5) after addingstainless steel metal balls and the metal powder at a weight ratio of15:1 in a stainless steel container. During the ball milling, argon wasinjected into the stainless steel container to provide an inertatmosphere.

After the ball milling, XRD analysis was performed in the same manner asin Example 1 to analyze the crystal structure. Also, a coin half cellwas prepared in the same manner as in Example 1 and then the batteryperformance was evaluated.

Comparative Example 1

Metal mass was prepared in the same manner as in Examples 1-5 exceptthat the metal material was melted by melt spinning and then annealedslowly in the air. The prepared metal mass was crushed manually in amortar to produce a metal powder, which was sieved so that the particlesize was not greater than 38 μm. The metal mass had a relatively higherratio of the crystalline phase than Examples 1-5. Phase analysis andbattery performance evaluation were carried out in the same manner as inExample 1.

The result of phase analysis and battery performance evaluation forExamples 1-5 and Comparative Example 1 is summarized in Table 3.

TABLE 3 Thickness Ratio of Maintenance of increase amorphous Electriccapacity after 50 after 50 phase capacity cycles* cycles** Ex. 1 46.6%  843 mAh/g 60% 257% Ex. 2 75% 835 mAh/g 65% 246% Ex. 3 81% 830 mAh/g 67%233% Ex. 4 89% 820 mAh/g 68% 211% Ex. 5 90% 816 mAh/g 75% 182% Comp. Ex.1 15% 875 mAh/g 5% 370% *= (Discharge capacity after 50 cycles/Dischargecapacity after 1 cycle) × 100 **= (Thickness after 50cycles-charging/Thickness before 1 cycle-charging) × 100

The contents of the crystalline and amorphous phases were determined byspiking. The spiking analysis of Example 1 was given earlier.

Evaluation Result:

In Examples 1-5, the ratio of the amorphous phase was 40% or greater.The electric capacity was superior (816-843 mAh/g) to carbonaceousmaterial (360 mAh/g) by 2 times or more. Also, maintenance of capacity(60-75%) was higher and volume expansion (182-257%) was less after 50cycles. In particular, as the ball milling proceeded, i.e. as the ratioof the amorphous phase increased, the electric capacity was decreased(from 843 mAh/g to 816 mAh/g), but maintenance of capacity was improved(from 60% to 75%) and volume expansion was decreased (from 257% to 182%)after 50 cycles.

In contrast, in Comparative Example 1, the crystalline phase was themajority (amorphous 15%, crystalline 85%). Although the electriccapacity was superior (875 mAh/g), maintenance of capacity (5%) was verylow and volume expansion was very large (370%) after 50 cycles.

Accordingly, it can be seen that as the ratio of the amorphous phaseincreases, the cycle characteristics become satisfactory and the volumeexpansion becomes controllable.

FIG. 3 shows the cycle characteristics of Examples 1-5 and ComparativeExample 1. As seen from FIG. 3, Examples 1-5 with larger ratio of theamorphous phase show better cycle characteristics than ComparativeExample 1 with larger ratio of the crystalline phase. Among Examples1-5, the cycle characteristics were better in the order of Example1<Example 2<Example 3<Example 4<Example 5. That is to say, the cyclecharacteristics were improved as the ratio of the amorphous phaseincreased.

Examples 6-10

A metal powder was prepared in the same manner as in Example 1 exceptfor mixing Si and Co at a weight ratio of 63:37 (Example 6). Thusprepared Si—Co alloy was prepared into a metal powder by ball milling inthe same manner as in Examples 2-5 (Examples 7-10). Then, phase analysisand battery performance evaluation were performed the same manner as inExample 1.

Comparative Example 2

A metal powder was prepared in the same manner as in Comparative Example1 except for mixing Si and Co at a weight ratio of 63:37. Then, phaseanalysis and battery performance evaluation were performed the samemanner as in Example 1.

Examples 11-15

A metal powder was prepared in the same manner as in Example 1 exceptfor mixing Si and Ni at a weight ratio of 65:35 (Example 11). Thusprepared Si—Ni alloy was prepared into a metal powder by ball milling inthe same manner as in Examples 2-5 (Examples 12-15) Then, phase analysisand battery performance evaluation were performed the same manner as inExample 1.

Comparative Example 3

A metal powder was prepared in the same manner as in Comparative Example1 except for mixing Si and Ni at a weight ratio of 65:35. Then, phaseanalysis and battery performance evaluation were performed the samemanner as in Example 1.

Examples 16-20

A metal powder was prepared in the same manner as in Example 1 exceptfor mixing Si and Mn at a weight ratio of 61:39 (Example 16). Thusprepared Si—Mn alloy was prepared into a metal powder by ball milling inthe same manner as in Examples 2-5 (Examples 17-20). Then, phaseanalysis and battery performance evaluation were performed the samemanner as in Example 1.

Comparative Example 4

A metal powder was prepared in the same manner as in Comparative Example1 except for mixing Si and Mn at a weight ratio of 61:39. Then, phaseanalysis and battery performance evaluation were performed the samemanner as in Example 1.

Examples 21-25

A metal powder was prepared in the same manner as in Example 1 exceptfor mixing Si, misch metal and Ni at a weight ratio of 57:15:28 (Example21). Thus prepared alloy was prepared into a metal powder by ballmilling in the same manner as in Examples 2-5 (Examples 22-25). Then,phase analysis and battery performance evaluation were performed thesame manner as in Example 1.

Comparative Example 5

A metal powder was prepared in the same manner as in Comparative Example1 except for mixing Si, misch metal and Ni at a weight ratio of57:15:28. Then, phase analysis and battery performance evaluation wereperformed the same manner as in Example 1.

The result of phase analysis and battery performance evaluation forExamples 6-25 and Comparative Examples 2-5 is shown in Table 4.

TABLE 4 Maintenance of Thickness Ratio of capacity increase amorphousElectric after 50 after 50 phase capacity cycles* cycles** Ex. 6 38% 987mAh/g 45% 296% Ex. 7 46% 976 mAh/g 51% 275% Ex. 8 49% 969 mAh/g 57% 266%Ex. 9 57% 967 mAh/g 59% 242% Ex. 10 64% 961 mAh/g 64% 239% Comp. Ex. 27% 1054 mAh/g  9% 390% Ex. 11 32% 1375 mAh/g  44% 317% Ex. 12 41% 1327mAh/g  47% 303% Ex. 13 49% 1319 mAh/g  53% 295% Ex. 14 55% 1275 mAh/g 57% 279% Ex. 15 57% 1266 mAh/g  60% 265% Comp. Ex. 3 4% 1458 mAh/g  4%413% Ex. 16 43% 955 mAh/g 57% 292% Ex. 17 71% 947 mAh/g 68% 277% Ex. 1876% 920 mAh/g 71% 268% Ex. 19 81% 913 mAh/g 72% 249% Ex. 20 88% 918mAh/g 74% 218% Comp. Ex. 4 13% 985 mAh/g 14% 381% Ex. 21 61% 1032 mAh/g 65% 245% Ex. 22 79% 978 mAh/g 69% 228% Ex. 23 83% 965 mAh/g 69% 219% Ex.24 88% 959 mAh/g 74% 202% Ex. 25 94% 952 mAh/g 77% 198% Comp. Ex. 5 27%1100 mAh/g  32% 366% *= (Discharge capacity after 50 cycles/Dischargecapacity after 1 cycle) × 100 **= (Thickness after 50cycles-charging/Thickness before 1 cycle-charging) × 100

Evaluation Result:

In Examples 6-25, the ratio of the amorphous phase was 30% or greater.The electric capacity was superior (913-1375 mAh/g) to carbonaceousmaterial (360 mAh/g) by 2.5 times or more. Also, maintenance of capacity(44-75%) was higher and volume expansion (198-317%) was less after 50cycles. In particular, as the ball milling proceeded, i.e. as the ratioof the amorphous phase increased, the cycle characteristics wereimproved and the volume expansion was reduced.

In contrast, in Comparative Examples 2-5, the crystalline phase was themajority, with the amorphous phase only 4-27%. Although the electriccapacity was superior (985-1458 mAh/g), maintenance of capacity (4-32%)was very low and volume expansion was very large (366-413%) after 50cycles.

Accordingly, it can be seen that as the ratio of the amorphous phaseincreases, the cycle characteristics become satisfactory and the volumeexpansion becomes controllable.

Examples 26-50

Anode active materials were prepared in the same manner as in Example 1except that the metal powders prepared in Examples 1-25 were mixedcarbon at a weight ratio of 50:50. Then, phase analysis and batteryperformance evaluation were performed the same manner as in Example 1.

Comparative Examples 6-10

Anode active materials were prepared in the same manner as in Example 1except that the metal powders prepared in Comparative Examples 1-5 weremixed with carbon at a weight ratio of 50:50. Then, phase analysis andbattery performance evaluation were performed the same manner as inExample 1.

The result of phase analysis and battery performance evaluation forExamples 26-50 and Comparative Examples 6-10 is shown in Table 5.

TABLE 5 Electric Thickness capacity Maintenance of capacity increase(mAh/g) after 50 cycles* after 50 cycles** Ex. 26 605 69 168 Ex. 27 59871 164 Ex. 28 594 74 161 Ex. 29 588 78 158 Ex. 30 586 79 154 Comp. Ex. 6619 31 226 Ex. 31 675 54 175 Ex. 32 670 59 168 Ex. 33 665 61 166 Ex. 34664 67 161 Ex. 35 661 75 156 Comp. Ex. 7 709 33 227 Ex. 36 865 49 156Ex. 37 841 54 151 Ex. 38 840 59 148 Ex. 39 821 64 147 Ex. 40 815 69 144Comp. Ex. 8 911 29 211 Ex. 41 655 66 159 Ex. 32 653 74 151 Ex. 33 640 77150 Ex. 44 637 79 147 Ex. 45 640 83 146 Comp. Ex. 9 674 41 223 Ex. 46671 73 141 Ex. 47 660 76 138 Ex. 48 659 78 138 Ex. 49 651 81 135 Ex. 50644 84 134 Comp. Ex. 10 732 49 194 *= (Discharge capacity after 50cycles/Discharge capacity after 1 cycle) × 100 **= (Thickness after 50cycles-charging/Thickness before 1 cycle-charging) × 100

Evaluation Result:

Examples 26-50 showed superior electric capacity was (585-865 mAh/g) ascompared to carbonaceous material (360 mAh/g). Also, maintenance ofcapacity (49-83%) was higher and volume expansion (134-168%) was lessafter 50 cycles.

In particular, as the ball milling proceeded, i.e. as the ratio of theamorphous phase increased, the cycle characteristics were improved andthe volume expansion was reduced.

In contrast, in Comparative Examples 6-10, although the electriccapacity was superior (619-911 mAh/g), maintenance of capacity (29-49%)was low and volume expansion was very large (194-227%) after 50 cycles.

In accordance with the present disclosure, an electrode exhibitingsuperior cycle characteristics, relatively less volume expansion andgood electric capacity can be prepared by controlling the ratio of thecrystalline phase and the amorphous phase in an anode active material.

While the present disclosure has been described with respect to thespecific embodiments, it will be apparent to those skilled in the artthat various changes and modifications may be made without departingfrom the spirit and scope of the disclosure as defined in the followingclaims.

What is claimed is:
 1. An anode active material comprising: acrystalline phase comprising Si and a Si-metal alloy; and an amorphousphase comprising Si and a Si-metal alloy, wherein the amorphous phase isincluded in an amount more than 30 wt %, and the metal of the Si-metalalloy of the crystalline phase is the same as or different from themetal of the Si-metal alloy of the amorphous phase.
 2. The anode activematerial according to claim 1, wherein the metal of the Si-metal alloyis one or more element selected from a group consisting of Ca, Sc, Ti,V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Y, Zr, Nb, Ba, Lu, Hf, Ta andlanthanides.
 3. The anode active material according to claim 1, wherein,in the Si-metal alloy of the crystalline phase and the Si-metal alloy ofthe amorphous phase, the metals of the alloys are the same.
 4. The anodeactive material according to claim 1, wherein, in the Si-metal alloy ofthe crystalline phase and the Si-metal alloy of the amorphous phase, themetal comprises one metal species.
 5. The anode active materialaccording to claim 1, wherein, in the Si-metal alloy of the crystallinephase and the Si-metal alloy of the amorphous phase, the metal comprisestwo metal species.
 6. The anode active material according to claim 4,wherein the metal is a metal selected from a group consisting of Co, Ni,Mn and Ti.
 7. The anode active material according to claim 5, whereinthe two metals comprise a metal selected from a group consisting of Tiand Zr and a metal selected from a group consisting of Co, Ni and Fe. 8.The anode active material according to claim 1, wherein, in the Si-metalalloy of the crystalline phase and the Si-metal alloy of the amorphousphase, the metal comprises one or more metal selected from rare earthelements and a metal selected from Co, Ni and Fe.
 9. An electrodecomprising the anode active material according to claim
 1. 10. Anelectrode comprising the anode active material according to claim 1 anda carbonaceous anode active material.
 11. A lithium secondary batterycomprising the electrode according to claim
 9. 12. A lithium secondarybattery comprising the electrode according to claim 10.